An antibacterial, high-temperature-resistant plastic particle and a preparation method thereof

Abstract

The application discloses an antibacterial and high-temperature-resistant plastic particle and a preparation method thereof, and belongs to the technical field of high polymer materials, and comprises the following components in weight parts: 80-90 parts of plastic master batch, 10-20 parts of antibacterial agent and 1-2 parts of plasticizer; the preparation method of the antibacterial and high-temperature-resistant plastic particle comprises the following steps: the plastic master batch, the antibacterial agent and the plasticizer are added into a mixer according to the weight parts of the formula, uniformly mixed, then transferred into a double-screw extruder for melt blending, extruded, cooled, and cut into particles; the antibacterial monomer containing quaternary phosphonium salt, the borneol acrylate monomer and the styrene monomer are matched according to a specific molar ratio, copolymerization is initiated by ultraviolet light, the antibacterial agent with antibacterial adhesion and antibacterial effects is obtained, and the antibacterial effect is durable; the addition of the styrene monomer can not only improve the thermal stability of the antibacterial agent, but also improve the mechanical properties of the plastic particle.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and particularly relates to an antibacterial and high-temperature-resistant plastic particle and a preparation method thereof. BACKGROUND

[0002] Plastic products have been widely used in people's daily life, such as household appliances, food packaging materials, home building materials, etc. The surface of the plastic products often has many bacteria, and some bacteria are harmful to the human body. When people come into contact with the plastic products, they are easily infected and diseased, so the plastic products are easy to become a medium for disease transmission, which threatens people's life and health. With the improvement of people's living standards and the increasing attention to health and safety issues, people hope to endow the plastic products commonly used in daily life with certain antibacterial properties, so as to reduce the possibility of bacterial contamination.

[0003] Antibacterial plastics mainly add inorganic antibacterial agents. There are few reports on the application of organic small-molecule antibacterial agents and high-molecular-weight antibacterial agents in plastics. The main reason is that the thermal stability of organic small-molecule antibacterial agents and high-molecular-weight antibacterial agents is poor, and it is difficult to withstand the high processing temperature of plastics. However, inorganic antibacterial agents have a dissolution effect. The antibacterial plastics prepared by adding inorganic antibacterial agents often have poor antibacterial durability, and there are potential safety problems. High-molecular-weight antibacterial agents have a non-dissolution antibacterial mechanism, which can overcome the shortcomings of the dissolution effect of inorganic antibacterial agents and organic small-molecule antibacterial agents, but the thermal stability needs to be improved. SUMMARY

[0004] The purpose of the present application is to provide an antibacterial and high-temperature-resistant plastic particle and a preparation method thereof, so as to solve the problem of how to make the plastic have good antibacterial property and high-temperature resistance.

[0005] The purpose of the present application can be achieved by the following technical solutions.

[0006] An antibacterial and high-temperature-resistant plastic particle comprises, by weight: 80-90 parts of plastic masterbatch, 10-20 parts of antibacterial agent, and 1-2 parts of plasticizer.

[0007] The antibacterial agent is prepared by the following steps:

[0008] Antibacterial monomers, bornyl acrylate monomers and styrene monomers are added to benzoin diethyl ether, stirred, mixed and dissolved, then poured into a tetrafluoroethylene flat mold, and the reaction is initiated under the irradiation of 254 nm ultraviolet light for 2-4 h. Then the reaction product is washed with tetrahydrofuran for 2-3 times by ultrasonic, and the unreacted monomers and oligomers are removed. The product is dried in a vacuum drying oven at 80℃ until the weight is constant, to obtain the antibacterial agent.

[0009] Further, the plastic masterbatch comprises any one of PP particles, PE particles and ABS particles.

[0010] Further, the molar ratio of the antibacterial monomer, the borneol acrylate monomer, the styrene monomer and the benzoin ethyl ether is 5-6:2-3:2:0.4-0.5.

[0011] Further, the antibacterial monomer is prepared by the following steps:

[0012] Step A1, 11-bromo-1-undecanol and triethylamine are added to dichloromethane and stirred to dissolve, then methyl acryloyl chloride is added dropwise under ice water bath condition, after the dropwise addition is completed, the ice water bath is removed and the reaction is stirred at room temperature for 10-12h, then rotary evaporation, column chromatography purification and drying to constant weight are performed to obtain intermediate 1.

[0013] Step A2, intermediate 1, triphenylphosphine and hydroquinone are added to acetonitrile and stirred to dissolve, then the temperature is raised to 80℃ for 20-24h, then rotary evaporation, column chromatography purification and drying to constant weight are performed to obtain the antibacterial monomer containing quaternary phosphonium salt in the molecular structure.

[0014] Further, the usage ratio of 11-bromo-1-undecanol, triethylamine, dichloromethane and methyl acryloyl chloride is 0.1-0.12mol:0.1-0.15mol:100mL:0.1-0.14mol.

[0015] Further, the usage ratio of intermediate 1, triphenylphosphine, hydroquinone and acetonitrile is 25-30g:25-30g:0.25-0.3g:100-150mL.

[0016] Further, the borneol acrylate monomer is prepared by the following steps:

[0017] L-borneol and triethylamine are added to tetrahydrofuran and stirred to dissolve, then acryloyl chloride is added dropwise under ice water bath condition, after the dropwise addition is completed, the reaction is stirred at room temperature for 10-12h, then tetrahydrofuran is removed by rotary evaporation to obtain the borneol acrylate monomer.

[0018] Further, the usage ratio of L-borneol, triethylamine, tetrahydrofuran and acryloyl chloride is 10g:9.6-9.8g:200mL:8.6-8.8g.

[0019] Further, the plasticizer is any one of triethyl citrate, tributyl citrate and diethylene glycol dibenzoate; the antibacterial agent contains a large number of rigid benzene rings, which will affect the plasticity of the plastic, so a plasticizer needs to be added to improve the plasticity of the plastic.

[0020] A preparation method of antibacterial and high-temperature-resistant plastic particles, comprising the following steps:

[0021] The plastic master batch, the antibacterial agent and the plasticizer are added into a mixer according to the weight parts of the formula, and then are uniformly mixed, and then are transferred into a double-screw extruder, and then are melt-blended at a temperature of 190-220 DEG C and a screw rotating speed of 80-100 r / min, and then are extruded, cooled and granulated, so that the antibacterial and high-temperature-resistant plastic particles are obtained.

[0022] The beneficial effects of the present application are as follows:

[0023] The present application uses levorotatory borneol and acryloyl chloride as raw materials, and the hydroxyl group of levorotatory borneol reacts with the acyl chloride of acryloyl chloride to prepare borneol acrylate monomer, which contains a chiral chemical structure that can be recognized by bacteria and stimulate bacteria to move away, thereby reducing the adhesion of bacteria on the surface of plastic products and achieving good antibacterial effect.

[0024] The present application uses 11-bromo-1-undecanol and methacryloyl chloride as raw materials, and the reaction produces intermediate 1 containing a long alkyl side chain, and then the intermediate 1 reacts with triphenylphosphine to obtain an antibacterial monomer containing a long alkyl side chain and a quaternary phosphonium salt structure, the long alkyl side chain can make the antibacterial monomer have more excellent antibacterial performance, and the antibacterial monomer contains a large number of phenyl groups, which can obtain an antibacterial monomer with more excellent thermal stability.

[0025] The present application combines the antibacterial monomer containing a quaternary phosphonium salt with borneol acrylate monomer and styrene monomer according to a specific molar ratio, and then copolymerizes them by ultraviolet light initiation to obtain an antibacterial agent with antibacterial adhesion and antibacterial effect, and the addition of styrene monomer can not only improve the thermal stability of the antibacterial agent, but also improve the mechanical properties of the plastic particles; the antibacterial agent is melt-blended with the plastic master batch to obtain plastic particles, on the one hand, the presence of borneol ester can reduce the adhesion of bacteria on the surface of the plastic, and reduce the possibility of bacterial breeding on the surface of the plastic; on the other hand, the quaternary phosphonium salt groups in the antibacterial monomer of the plastic particles migrate to the surface of the plastic due to the polar repulsion, so that more quaternary phosphonium salt groups are exposed on the surface of the plastic to play an antibacterial role, thereby enhancing the antibacterial performance of the plastic particles, and the antibacterial monomer will not migrate out of the plastic matrix with the passage of time, thereby having more durable antibacterial properties. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0027] Embodiment 1

[0028] The present embodiment provides an antibacterial monomer, which is prepared by the following steps:

[0029] Step A1, 25g 11-bromo-1-undecanol and 10.2g triethylamine were added into 100mL dichloromethane and stirred to dissolve, 10.5g methacryloyl chloride was added dropwise under ice water bath condition, after the dropwise addition was completed, the ice water bath was removed and the reaction was stirred at room temperature for 10h, dichloromethane was removed by rotary evaporation to obtain a concentrated solution, the concentrated solution was purified by column chromatography to obtain an eluate, the eluate was rotary evaporated to remove the solvent, and then dried to constant weight in a vacuum drying oven to obtain intermediate 1;

[0030] Step A2, 25g of intermediate 1, 25g of triphenylphosphine and 0.25g of hydroquinone were added into 100mL acetonitrile and stirred to dissolve, then heated to 80°C and incubated for 20h, acetonitrile was removed by rotary evaporation, the concentrated solution was purified by column chromatography to obtain an eluate, the eluate was rotary evaporated to remove the solvent, and then dried to constant weight in a vacuum drying oven to obtain an antibacterial monomer.

[0031] Example 2

[0032] This example provides an antibacterial monomer, which is prepared by the following steps:

[0033] Step A1, 25g 11-bromo-1-undecanol and 10.2g triethylamine were added into 100mL dichloromethane and stirred to dissolve, 10.5g methacryloyl chloride was added dropwise under ice water bath condition, after the dropwise addition was completed, the ice water bath was removed and the reaction was stirred at room temperature for 10h, dichloromethane was removed by rotary evaporation to obtain a concentrated solution, the concentrated solution was purified by column chromatography to obtain an eluate, the eluate was rotary evaporated to remove the solvent, and then dried to constant weight in a vacuum drying oven to obtain intermediate 1;

[0034] Step A2, 25g of intermediate 1, 25g of triphenylphosphine and 0.25g of hydroquinone were added into 100mL acetonitrile and stirred to dissolve, then heated to 80°C and incubated for 20h, acetonitrile was removed by rotary evaporation, the concentrated solution was purified by column chromatography to obtain an eluate, the eluate was rotary evaporated to remove the solvent, and then dried to constant weight in a vacuum drying oven to obtain an antibacterial monomer.

[0035] Example 3

[0036] This example provides an antibacterial monomer, which is prepared by the following steps:

[0037] Step A1, 30g of 11-bromo-1-undecanol and 15g of triethylamine were added into 100mL of dichloromethane and stirred to dissolve, 14.6g of methacryloyl chloride was added dropwise under ice water bath condition, after the addition was completed, the ice water bath was removed and the reaction was stirred at room temperature for 12h, dichloromethane was removed by rotary evaporation to obtain a concentrated solution, the concentrated solution was purified by column chromatography to obtain an eluate, the eluate was rotary evaporated to remove the solvent, and then dried to constant weight in a vacuum drying oven to obtain intermediate 1;

[0038] Step A2, 30g of intermediate 1, 30g of triphenylphosphine and 0.3g of hydroquinone were added into 150mL of acetonitrile and stirred to dissolve, then heated to 80℃ for 24h, acetonitrile was removed by rotary evaporation, the concentrated solution was purified by column chromatography to obtain an eluate, the eluate was rotary evaporated to remove the solvent, and then dried to constant weight in a vacuum drying oven to obtain an antibacterial monomer.

[0039] Example 4

[0040] This example provides a borneol acrylate monomer, which is prepared by the following steps:

[0041] 10g of levorotatory borneol and 9.6g of triethylamine were added into 200mL of tetrahydrofuran and stirred to dissolve, then 8.6g of acryloyl chloride was added dropwise under ice water bath condition, after the addition was completed, the reaction was stirred at room temperature for 10h, and then tetrahydrofuran was removed by rotary evaporation to obtain a borneol acrylate monomer.

[0042] Example 5

[0043] This example provides a borneol acrylate monomer, which is prepared by the following steps:

[0044] 10g of levorotatory borneol and 9.8g of triethylamine were added into 200mL of tetrahydrofuran and stirred to dissolve, then 8.8g of acryloyl chloride was added dropwise under ice water bath condition, after the addition was completed, the reaction was stirred at room temperature for 12h, and then tetrahydrofuran was removed by rotary evaporation to obtain a borneol acrylate monomer.

[0045] Example 6

[0046] This example provides an antibacterial agent, which is prepared by the following steps:

[0047] The antibacterial monomer prepared in Example 1, the borneol acrylate monomer prepared in Example 4 and styrene monomer were added into benzoin diethyl ether according to a molar ratio of 5:3:2:0.4, stirred and mixed to dissolve, then poured into a tetrafluoroethylene flat mold, and initiated to react under 254nm ultraviolet light for 2h, then the reaction product was washed with tetrahydrofuran for 2 times to remove unreacted monomers and oligomers, and dried to constant weight in a vacuum drying oven at 80℃ to obtain an antibacterial agent.

[0048] Example 7

[0049] The present example provides an antibacterial agent, which is prepared by the following steps:

[0050] The antibacterial monomer prepared in Example 2, the bornyl acrylate monomer prepared in Example 5 and the styrene monomer are added into benzene in a molar ratio of 5.5:2.5:2:0.5, stirred and mixed to dissolve, then poured into a teflone flat mold, and the reaction is initiated under irradiation of 254 nm ultraviolet light for 3 h. Then the reaction product is washed with tetrahydrofuran for 3 times by ultrasonic to remove the unreacted monomers and oligomers, and dried in a vacuum drying oven at 80°C to constant weight to obtain the antibacterial agent.

[0051] Example 8

[0052] The present example provides an antibacterial agent, which is prepared by the following steps:

[0053] The antibacterial monomer prepared in Example 3, the bornyl acrylate monomer prepared in Example 5 and the styrene monomer are added into benzene in a molar ratio of 6:2:2:0.5, stirred and mixed to dissolve, then poured into a teflone flat mold, and the reaction is initiated under irradiation of 254 nm ultraviolet light for 4 h. Then the reaction product is washed with tetrahydrofuran for 3 times by ultrasonic to remove the unreacted monomers and oligomers, and dried in a vacuum drying oven at 80°C to constant weight to obtain the antibacterial agent.

[0054] Comparative Example 1

[0055] The present comparative example is the same as Example 8 except that no antibacterial monomer is added.

[0056] Comparative Example 2

[0057] The present comparative example is the same as Example 8 except that no bornyl acrylate monomer is added.

[0058] Comparative Example 3

[0059] The present comparative example is the same as Example 8 except that no styrene monomer is added.

[0060] Example 9

[0061] The present example provides an antibacterial and high-temperature-resistant plastic particle, which is prepared by the following preparation method:

[0062] 80 parts by weight of PP particles, 10 parts by weight of the antibacterial agent prepared in Example 6 and 1 part by weight of triethyl citrate are added into a mixer and mixed uniformly, then transferred into a twin-screw extruder, and melt blended at a temperature of 200°C and a screw rotation speed of 90 r / min. After extrusion, cooling and granulation, the antibacterial and high-temperature-resistant plastic particle is obtained.

[0063] Example 10

[0064] The embodiment provides an antibacterial and high-temperature-resistant plastic particle, which is prepared by the following preparation method.

[0065] 85 parts by weight of PE particles, 15 parts by weight of the antibacterial agent prepared in Example 7 and 1.5 parts by weight of tributyl citrate are added into a mixer and uniformly mixed, and then transferred into a double-screw extruder, melt blending is carried out at a temperature of 190 DEG C and a screw rotation speed of 80 r / min, and after extrusion, cooling and granulation, the antibacterial and high-temperature-resistant plastic particle is obtained.

[0066] Example 11

[0067] The embodiment provides an antibacterial and high-temperature-resistant plastic particle, which is prepared by the following preparation method.

[0068] 90 parts by weight of ABS particles, 20 parts by weight of the antibacterial agent prepared in Example 8 and 2 parts by weight of diethylene glycol dibenzoate are added into a mixer and uniformly mixed, and then transferred into a double-screw extruder, melt blending is carried out at a temperature of 220 DEG C and a screw rotation speed of 100 r / min, and after extrusion, cooling and granulation, the antibacterial and high-temperature-resistant plastic particle is obtained.

[0069] Comparative Example 4

[0070] Compared with Example 11, the antibacterial agent prepared in Comparative Example 1 is used to replace the antibacterial agent prepared in Example 8, and the remaining raw materials and steps are the same.

[0071] Comparative Example 5

[0072] Compared with Example 11, the antibacterial agent prepared in Comparative Example 2 is used to replace the antibacterial agent prepared in Example 8, and the remaining raw materials and steps are the same.

[0073] Comparative Example 6

[0074] Compared with Example 11, the antibacterial agent prepared in Comparative Example 3 is used to replace the antibacterial agent prepared in Example 8, and the remaining raw materials and steps are the same.

[0075] The plastic particles prepared in Example 9-Example 11 and Comparative Example 4-Comparative Example 6 are subjected to performance testing, a thermogravimetric analyzer is used to test the temperature T of the plastic particles when the thermal degradation mass reaches 5%, the tensile property is tested according to GB / T 1040.2-2022, the tensile rate is 200 mm / min, the bending strength is tested according to GB / T9341-2008, the bending rate is 2 mm / min, the antibacterial property is tested according to GB / T 31402-2015, the antibacterial rates of the plastic samples without water soaking and after water soaking for 30 days on escherichia coli and staphylococcus aureus are tested through a biochemical incubator, and the results are shown in Table 1. 5％ ; the tensile property is tested according to GB / T 1040.2-2022, the tensile rate is 200 mm / min; the bending strength is tested according to GB / T9341-2008, the bending rate is 2 mm / min; the antibacterial property is tested according to GB / T 31402-2015, the antibacterial rates of the plastic samples without water soaking and after water soaking for 30 days on escherichia coli and staphylococcus aureus are tested through a biochemical incubator, and the results are shown in Table 1:

[0076] Table 1

[0077]

[0078] As can be seen from the data in Table 1, the plastic particles prepared in Examples 9-11 have more excellent thermal stability, mechanical strength, antibacterial property and antibacterial durability, and the antibacterial monomer, the bornyl acrylate monomer and the styrene monomer synergistically act to improve the antibacterial and high-temperature resistant properties of the plastic particles.

[0079] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting; it is not intended to exclude myriad other embodiments of the present application that are not specifically enumerated herein. In this document, relational terms such as first and second and the like can be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. Furthermore, no limitation arising from the description of an embodiment using terminology such as "comprising", "comprising", or "including" with respect to a given list of elements will apply to the embodiments of the present application unless otherwise claimed.

[0080] While the embodiments of the present application have been shown and described, it is to be understood that the embodiments can be varied, modified, substituted and otherwise changed without departing from the principles and spirit of the application, and the scope of the application is to be limited only by the claims and equivalents thereof.

Claims

1. An antibacterial, high-temperature resistant plastic particle, characterized in that, By weight parts including: plastic masterbatch 80-90 parts, antibacterial agent 10-20 parts, plasticizer 1-2 parts; The antibacterial agent is prepared by the following steps: The antibacterial monomer, bornyl acrylate monomer and styrene monomer are added to benzene diethyl ether, the molar ratio of the antibacterial monomer, bornyl acrylate monomer, styrene monomer and benzene diethyl ether is 5-6:2-3:2:0.4-0.5, after stirring, mixing and dissolving, pour into a teflone flat mold, initiate the reaction under 254nm ultraviolet light for 2-4h, then wash the reaction product with tetrahydrofuran for 2-3 times, dry in a vacuum drying oven until constant weight, to obtain the antibacterial agent; The antibacterial monomer is prepared by the following steps: Step A1, 11-bromo-1-undecanol and triethylamine are added to dichloromethane and stirred to dissolve, then add methacryloyl chloride dropwise under ice water bath condition, after the dropwise addition is completed, remove the ice water bath and stir at room temperature for 10-12h, after rotary evaporation, column chromatography purification and drying to constant weight, obtain intermediate 1; Step A2, intermediate 1, triphenylphosphine and hydroquinone are added to acetonitrile and stirred to dissolve, then heat to 80℃ and keep for 20-24h, after rotary evaporation, column chromatography purification and drying to constant weight, obtain the antibacterial monomer.

2. The antibacterial, high-temperature resistant plastic granule according to claim 1, characterized in that, The plastic masterbatch includes any one of PP particles, PE particles and ABS particles.

3. The antibacterial, high-temperature resistant plastic granule according to claim 1, characterized in that, The amount ratio of 11-bromo-1-undecanol, triethylamine, dichloromethane and methacryloyl chloride is 0.1-0.12mol:0.1-0.15mol:100mL:0.1-0.14mol.

4. The antibacterial, high-temperature resistant plastic granule according to claim 1, characterized in that, The amount ratio of intermediate 1, triphenylphosphine, hydroquinone and acetonitrile is 25-30g:25-30g:0.25-0.3g:100-150mL.

5. The antimicrobial, high temperature resistant plastic granule according to claim 1, wherein, The bornyl acrylate monomer is prepared by the following steps: L-levo-borneol and triethylamine are added to tetrahydrofuran and stirred to dissolve, then add acryloyl chloride dropwise under ice water bath condition, after the dropwise addition is completed, stir at room temperature for 10-12h, after removing tetrahydrofuran by rotary evaporation, obtain the bornyl acrylate monomer.

6. The antibacterial, high-temperature resistant plastic granule according to claim 5, characterized in that, The amount ratio of L-levo-borneol, triethylamine, tetrahydrofuran and acryloyl chloride is 10g:9.6-9.8g:200mL:8.6-8.8g.

7. The antimicrobial, high temperature resistant plastic granule according to claim 1, wherein, The plasticizer is any one of triethyl citrate, tributyl citrate and diethylene glycol dibenzoate.

8. The method for preparing antibacterial and high-temperature resistant plastic granules according to claim 1, characterized in that, The following steps are included: According to the formula weight parts, the plastic masterbatch, the antibacterial agent and the plasticizer are added to a mixer and mixed uniformly, then transferred into a twin-screw extruder for melt blending, after extrusion, cooling and granulation, obtain antibacterial and high-temperature resistant plastic particles.

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