An antibacterial polystyrene composite material and a preparation method thereof

Abstract

The application discloses an antibacterial polystyrene composite material which is prepared from the following components in parts by weight: 80-100 parts of PS, 8-12 parts of PS composite material and 0.1-0.5 parts of antioxidant. The PS composite material contains PS, SiO2 and Cu in the structure, wherein the silicon dioxide generates cavities under ultraviolet light irradiation, can react with water molecules to generate high-activity free radicals (·OH), the photo-generated electrons can react with O2 to generate ·OH, and when the electrons are transmitted to the surface of nano Cu, the free radicals are generated by capturing O2 on the surface of Cu. The silicon dioxide and the surface of Cu of the PS composite material can generate high-activity free radicals, so that organic matters are completely oxidized and degraded, the cell membranes can be penetrated, the membrane structure can be damaged and bacteria can be killed, and the bactericidal effect is achieved. In addition, the SiO2 in the PS composite material can also be used as a reinforcing filler to improve the physical properties of the antibacterial polystyrene composite material.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, specifically relating to an antibacterial polystyrene composite material and its preparation method. Background Technology

[0002] Polystyrene (PS) is lightweight, non-toxic, odorless, and chemically stable, and is insoluble in common solvents at room temperature. Although PS has excellent overall properties, its antibacterial and physical properties are only average, limiting the application of PS composites.

[0003] For this reason, the present invention innovatively produces a PS composite material with excellent antibacterial and physical properties, which makes up for the shortcomings of existing PS composite materials and expands the application range of PS composite materials. Summary of the Invention

[0004] This invention innovatively synthesizes a high-performance antibacterial PS composite material, which has excellent mechanical and antibacterial properties, solving the technical problem of limited mechanical and antibacterial properties of PS in existing technologies.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] An antibacterial polystyrene composite material is prepared from the following components in parts by weight:

[0007] PS 80-100 parts, PS composite material 8-12 parts, antioxidant 0.1-0.5 parts;

[0008] The preparation method of the PS composite material is as follows:

[0009] (1) Styrene, deionized water, initiator, ethanol, and orthosilicate compounds are added to a reactor vessel and reacted at 50-70℃ for 10-12 h to obtain reactant A; further, the initiator is sodium persulfate; the orthosilicate compound is butyl orthosilicate; the mass ratio of styrene, deionized water, sodium persulfate, anhydrous ethanol, and butyl orthosilicate is (40-60):(180-240):(0.1-0.3):(30-40):(16-20). This step involves the following chemical reactions: on the one hand, styrene undergoes polymerization under the action of the initiator to produce polystyrene (PS); on the other hand, the orthosilicate compound undergoes hydrolysis to produce SiO2; since the above reactions are carried out in the same reaction system, the generated SiO2 can adhere to the PS surface in situ, and the products have good adsorption force, which improves the stability of the product structure.

[0010] (2) The reactant A was filtered and the solid material was collected. After washing, the solid material was dried at 40-60℃ for 4-6 hours to obtain sample B.

[0011] (3) Cool sample B to room temperature to obtain PS / SiO2 composite material.

[0012] (4) Add the PS / SiO2 composite material, deionized water, copper salt, alkaline solution, and reducing agent to a reactor vessel and react at 40-60℃ for 8-10 hours. Filter the reaction product and collect the solid material. After washing, dry the solid material at 40-60℃ for 4-6 hours to obtain the PS / SiO2 / Cu composite material, which is the PS composite material. Further, the reducing agent is sodium borohydride; the copper salt is copper nitrate, copper sulfate, or copper phosphate; the alkaline solution is ammonia or sodium hydroxide solution with a concentration of 30%-40%; the mass ratio of the PS / SiO2 composite material, deionized water, copper salt, alkaline solution, and sodium borohydride is (30-40):(160-200):(12-16):(10-18):(0.2-0.6).

[0013] The antioxidant is at least one of antioxidant 168, antioxidant 1010, and antioxidant 1330.

[0014] This invention also discloses a method for preparing the above-mentioned antibacterial polystyrene composite material, comprising the following steps:

[0015] (1) Weigh 80-100 parts of PS, 8-12 parts of PS composite material, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture;

[0016] (2) The mixture obtained in step (1) is melt-extruded using a twin-screw extruder and then granulated to obtain the antibacterial polystyrene composite material. Preferably, the twin-screw extruder includes six temperature zones arranged in sequence, as follows: Zone 1 temperature 160-180℃, Zone 2 temperature 210-250℃, Zone 3 temperature 210-250℃, Zone 4 temperature 210-250℃, Zone 5 temperature 210-250℃, and Zone 6 temperature 210-250℃; the die temperature of the twin-screw extruder is 210-250℃, and the screw speed is 200-280 r / min.

[0017] Compared with the prior art, the beneficial effects of the present invention are reflected in:

[0018] 1. The PS composite material prepared in this scheme is a complex of PS, SiO2, and Cu. Silica generates holes under ultraviolet light irradiation, which can react with water molecules in the air to generate highly reactive free radicals (·OH). Photogenerated electrons can react with O2 in the air to generate (·OH), and when electrons are transferred to the surface of nano-Cu, they capture O2 on the Cu surface to generate free radicals. Both the silica and Cu surfaces in this PS composite material can generate highly reactive free radicals. The ·OH free radicals have strong oxidizing power, causing complete oxidation and degradation of organic matter. They can also penetrate cell membranes, destroy membrane structures, and kill bacteria, achieving a bactericidal effect.

[0019] 2. This scheme innovatively synthesizes a PS composite material with antibacterial effect. Since it contains PS components, based on the principle of similar compatibility, it has good interfacial compatibility with PS resin matrix. After mixing it with PS resin matrix, it can significantly improve the antibacterial performance of the material. In addition, SiO2 in PS composite material can also be used as a reinforcing filler to improve the physical properties of antibacterial polystyrene composite material. Detailed Implementation

[0020] To facilitate understanding of the present invention, a more comprehensive description of the invention will be provided below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to enable a more thorough and complete understanding of the disclosure of the present invention.

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0022] The raw materials used in the following examples are as follows:

[0023] PS (model SKH-127), SK Korea;

[0024] Deionized water, Shanghai LianShi Chemical Reagent Co., Ltd.

[0025] Copper nitrate, Henan Fushida Chemical Products Co., Ltd.;

[0026] Styrene, Jinan Linsheng Chemical Co., Ltd.;

[0027] Sodium persulfate, Shandong Chuangying Chemical Co., Ltd.;

[0028] Anhydrous ethanol, Wuhan Xiangheyi Chemical Technology Co., Ltd.

[0029] Butyl orthosilicate, Shandong Mingyue Chemical Co., Ltd.;

[0030] Ammonia water, Guangxi Yiping Chemical Co., Ltd.;

[0031] Sodium borohydride, Guangdong Leyuan Chemical Materials Technology Co., Ltd.;

[0032] Antioxidants (models Irganox 168, Irganox 1010, Irganox 1330), BASF, Germany.

[0033] In addition, unless otherwise specified, the preparation processes in the following embodiments are all conventional methods in the prior art, and therefore will not be described in detail; the parts in the following embodiments refer to parts by weight.

[0034] Preparation Example 1

[0035] The preparation method of PS composite material is as follows:

[0036] (1) Weigh 400g styrene, 1.8kg deionized water, 1g sodium persulfate, 300g anhydrous ethanol and 160g tetrabutyl orthosilicate, add them to a reactor vessel, and react at 50℃ for 10h to obtain solution A.

[0037] (2) Wash, filter and dry at 40°C for 4 hours to obtain sample B.

[0038] (3) Cool sample B to room temperature and pass it through a 500-mesh sieve to obtain the PS / SiO2 composite material.

[0039] (4) Weigh 300g of PS / SiO2 composite material, 1.6kg of deionized water, 120g of copper nitrate, 100g of ammonia water and 2g of sodium borohydride reducing agent, add them to a reactor vessel, react at 40℃ for 8h, wash, filter and dry at 40℃ for 4h to obtain PS composite material, denoted as M1.

[0040] Example 1

[0041] The preparation method of antibacterial polystyrene composite material includes the following steps:

[0042] (1) Weigh 80 parts of PS, 8 parts of PS composite material M1, and 0.1 parts of Irganox168, mix and stir evenly to obtain a mixture;

[0043] (2) The mixture obtained in step (1) is extruded and granulated to obtain the antibacterial polystyrene composite material, denoted as P1.

[0044] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1: 160℃, Zone 2: 210℃, Zone 3: 210℃, Zone 4: 210℃, Zone 5: 210℃, Zone 6: 210℃, Die head: 210℃, and screw speed: 200 r / min.

[0045] Preparation Example 2

[0046] The preparation method of PS composite material is as follows:

[0047] (1) Weigh 600g styrene, 2.4kg deionized water, 3g sodium persulfate, 400g anhydrous ethanol and 200g tetrabutyl orthosilicate, add them to a reactor vessel, and react at 70℃ for 12h to obtain solution A.

[0048] (2) Wash, filter and dry at 60°C for 6 hours to obtain sample B.

[0049] (3) Cool sample B to room temperature and pass it through a 500-mesh sieve to obtain the PS / SiO2 composite material.

[0050] (4) Weigh 400g of PS / SiO2 composite material, 2.0kg of deionized water, 160g of copper nitrate, 180g of ammonia water and 6g of sodium borohydride reducing agent, add them to a reactor vessel, react at 60℃ for 10h, wash, filter and dry at 60℃ for 6h to obtain PS composite material, denoted as M2.

[0051] Example 2

[0052] The preparation method of antibacterial polystyrene composite material includes the following steps:

[0053] (1) Weigh 100 parts of PS, 12 parts of PS composite material M2, 0.1 parts of Irganox168, 0.2 parts of Irganox1010, and 0.2 parts of Irganox1330, mix and stir evenly to obtain a mixture;

[0054] (2) The mixture obtained in step (1) is extruded and granulated to obtain the antibacterial polystyrene composite material, denoted as P2.

[0055] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1: 180℃, Zone 2: 250℃, Zone 3: 250℃, Zone 4: 250℃, Zone 5: 250℃, Zone 6: 250℃, Die head: 250℃, and screw speed: 280 r / min.

[0056] Preparation Example 3

[0057] The preparation method of PS composite material is as follows:

[0058] (1) Weigh 500g styrene, 2.1kg deionized water, 2g sodium persulfate, 350g anhydrous ethanol and 180g tetrabutyl orthosilicate, add them to a reactor vessel, and react at 60℃ for 11h to obtain solution A.

[0059] (2) Wash, filter, and dry at 50°C for 5 hours to obtain sample B.

[0060] (3) Cool sample B to room temperature and pass it through a 500-mesh sieve to obtain the PS / SiO2 composite material.

[0061] (3) Weigh 350g of PS / SiO2 composite material, 1.8kg of deionized water, 140g of copper nitrate, 140g of ammonia water and 4g of sodium borohydride reducing agent, add them to a reactor vessel, react at 50℃ for 9h, wash, filter and dry at 50℃ for 5h to obtain PS composite material, denoted as M3.

[0062] Example 3

[0063] The preparation method of antibacterial polystyrene composite material includes the following steps:

[0064] (1) Weigh 90 parts of PS, 10 parts of PS composite material M3, 0.1 parts of Irganox168, and 0.2 parts of Irganox1010, mix and stir evenly to obtain a mixture;

[0065] (2) The mixture obtained in step (1) is extruded and granulated to obtain antibacterial polystyrene composite material, denoted as P3.

[0066] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1: 170℃, Zone 2: 230℃, Zone 3: 230℃, Zone 4: 230℃, Zone 5: 230℃, Zone 6: 230℃, Die head: 230℃, and screw speed: 240 r / min.

[0067] Preparation Example 4

[0068] The preparation method of PS composite material is as follows:

[0069] (1) Weigh 480g styrene, 2.2kg deionized water, 2g sodium persulfate, 380g anhydrous ethanol and 195g tetrabutyl orthosilicate, add them to a reactor vessel, and react at 55℃ for 10h to obtain solution A.

[0070] (2) Wash, filter and dry at 45°C for 6 hours to obtain sample B.

[0071] (3) Cool sample B to room temperature and pass it through a 500-mesh sieve to obtain the PS / SiO2 composite material.

[0072] (4) Weigh 380g of PS / SiO2 composite material, 1.9kg of deionized water, 150g of copper nitrate, 175g of ammonia water and 5g of sodium borohydride reducing agent, add them to a reactor vessel, react at 45℃ for 9h, wash, filter and dry at 45℃ for 4h to obtain PS / SiO2 / Cu composite material, which is PS composite material, denoted as M4.

[0073] Example 4

[0074] The preparation method of antibacterial polystyrene composite material includes the following steps:

[0075] (1) Weigh 85 parts of PS, 11 parts of PS composite material M4, 0.1 parts of Irganox1010, and 0.2 parts of Irganox1330, mix and stir evenly to obtain a mixture;

[0076] (2) The mixture obtained in step (1) is extruded and granulated to obtain the antibacterial polystyrene composite material, denoted as P4.

[0077] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1 temperature 165℃, Zone 2 temperature 215℃, Zone 3 temperature 215℃, Zone 4 temperature 215℃, Zone 5 temperature 215℃, Zone 6 temperature 215℃, Die head temperature 215℃, and screw speed 210r / min.

[0078] Preparation Example 5

[0079] The preparation method of PS composite material is as follows:

[0080] (1) Weigh 580g styrene, 2.3kg deionized water, 3g sodium persulfate, 370g anhydrous ethanol and 165g tetrabutyl orthosilicate, add them to a reactor vessel, and react at 65℃ for 10h to obtain solution A.

[0081] (2) Wash, filter and dry at 45°C for 6 hours to obtain sample B.

[0082] (3) Cool sample B to room temperature and pass it through a 500-mesh sieve to obtain the PS / SiO2 composite material.

[0083] (4) Weigh 395g of PS / SiO2 composite material, 1.85kg of deionized water, 150g of copper nitrate, 175g of ammonia water and 5g of sodium borohydride reducing agent, add them to a reactor vessel, react at 46℃ for 9h, wash, filter, dry at 48℃ for 5h to obtain PS composite material, denoted as M5.

[0084] Example 5

[0085] The preparation method of antibacterial polystyrene composite material includes the following steps:

[0086] (1) Weigh 95 parts of PS, 8 parts of PS composite material M5, 0.2 parts of Irganox1010, and 0.2 parts of Irganox1330, mix and stir evenly to obtain a mixture;

[0087] (2) The mixture obtained in step (1) is extruded and granulated to obtain antibacterial polystyrene composite material, denoted as P5.

[0088] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1: 175℃, Zone 2: 235℃, Zone 3: 235℃, Zone 4: 235℃, Zone 5: 235℃, Zone 6: 235℃, Die head: 235℃, and screw speed: 245 r / min.

[0089] Comparative Example 1

[0090] The preparation method of PS composite material includes the following steps:

[0091] (1) Weigh 95 parts of PS, 0.2 parts of Irganox1010, and 0.2 parts of Irganox1330, mix and stir evenly to obtain a mixture;

[0092] (2) The mixture obtained in step (1) is extruded and granulated to obtain the PS composite material, denoted as D1.

[0093] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1: 175℃, Zone 2: 235℃, Zone 3: 235℃, Zone 4: 235℃, Zone 5: 235℃, Zone 6: 235℃, Die head: 235℃, and screw speed: 245 r / min.

[0094] Comparative Example 2

[0095] The preparation method of PS composite material includes the following steps:

[0096] (1) Weigh 95 parts of PS, 8 parts of silver-based antibacterial agent MT-T-110, 0.2 parts of Irganox1010, and 0.2 parts of Irganox1330, mix and stir evenly to obtain a mixture;

[0097] (2) The mixture obtained in step (1) is extruded and granulated to obtain the PS composite material, denoted as D2.

[0098] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1: 175℃, Zone 2: 235℃, Zone 3: 235℃, Zone 4: 235℃, Zone 5: 235℃, Zone 6: 235℃, Die head: 235℃, and screw speed: 245 r / min.

[0099] Comparative Example 3

[0100] The preparation method of PS composite material includes the following steps:

[0101] (1) Weigh 95 parts of PS, 8 parts of SiO2 microspheres, 0.2 parts of Irganox1010, and 0.2 parts of Irganox1330, mix and stir evenly to obtain a mixture;

[0102] (2) The mixture obtained in step (1) is extruded and granulated to obtain the PS composite material, denoted as D3.

[0103] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1: 175℃, Zone 2: 235℃, Zone 3: 235℃, Zone 4: 235℃, Zone 5: 235℃, Zone 6: 235℃, Die head: 235℃, and screw speed: 245 r / min.

[0104] Comparative Example 4

[0105] The preparation method of PS composite material includes the following steps:

[0106] (1) Weigh 380g styrene, 1.7kg deionized water, 3g sodium persulfate, 370g anhydrous ethanol and 165g tetrabutyl orthosilicate, add them to a reactor vessel, and react at 65℃ for 10h to obtain solution A.

[0107] (2) Wash, filter and dry at 45°C for 6 hours to obtain sample B.

[0108] (3) Place sample B in a muffle furnace and calcine at 635°C for 11 hours. Cool to room temperature and pass through a 500-mesh sieve to obtain the PS / SiO2 composite material.

[0109] (4) Weigh 395g of PS / SiO2 composite material, 1.85kg of deionized water, 150g of copper nitrate, 175g of ammonia water and 5g of sodium borohydride reducing agent, add them to a reactor vessel, react at 46℃ for 9h, wash, filter, dry at 48℃ for 5h to obtain PS composite material, denoted as N.

[0110] (5) Weigh 95 parts of PS, 8 parts of PS composite material N, 0.2 parts of Irganox1010, and 0.2 parts of Irganox1330, mix and stir evenly to obtain a mixture;

[0111] (6) The mixture obtained in step (5) is extruded and granulated to obtain the PS composite material, denoted as D4.

[0112] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1: 175℃, Zone 2: 235℃, Zone 3: 235℃, Zone 4: 235℃, Zone 5: 235℃, Zone 6: 235℃, Die head: 235℃, and screw speed: 245 r / min.

[0113] The antibacterial rate, tensile strength, and flexural modulus of the products obtained in the above embodiments and comparative examples were tested. The test standards and related conditions for each test are as follows:

[0114] The antibacterial rate test was conducted according to standard JIS Z 2801, using test pieces with a specification of (50mm±2mm)×(50mm±2mm)×(6mm±0.1mm), and the test was conducted 24 hours after inoculation.

[0115] Tensile strength testing was conducted according to standard ASTM D638. The tensile specimen used for testing was (170.0±5.0)mm*(13.0±0.5)mm*(3.2±0.2)mm, and the tensile rate was 5mm / min.

[0116] The flexural modulus test was conducted according to ASTM D790 standard. The test bending specimen was (125.0±5.0)mm*(13.0±0.5)mm*(3.2±0.2)mm, and the bending rate was 1.25mm / min.

[0117] The test results are shown in Table 1 below:

[0118] Table 1. Performance test results of PS composite materials prepared in each embodiment and comparative example.

[0119]

[0120] As can be seen from the table, the antibacterial properties and physical properties of Examples 1-5 are better than those of Comparative Examples 1-4. This indicates that the PS composite material of this invention has better antibacterial and mechanical properties than ordinary PS material, PS with silver-based antibacterial agent MT-T-110, PS with ordinary silica, and PS composite materials with other proportions.

[0121] This invention yields a PS composite material with excellent antibacterial and physical properties, which overcomes the shortcomings of existing materials and expands the application field of PS composite materials.

[0122] The above-disclosed embodiments are only a few specific examples of this application, but this application is not limited thereto. Any variations that can be conceived by those skilled in the art should fall within the protection scope of this application.

Claims

1. An antibacterial polystyrene composite material, characterized in that: It is prepared from the following components in parts by weight: PS 80-100 parts, PS composite material 8-12 parts, antioxidant 0.1-0.5 parts; The preparation method of the PS composite material is as follows: (1) Styrene, deionized water, initiator, ethanol and orthosilicate compound are added to a reactor vessel and reacted at 50-70℃ for 10-12h to obtain reactant A; (2) The reactant A was filtered and the solid material was collected. After washing and drying, the solid material was used to obtain sample B. (3) Cool sample B to room temperature to obtain PS / SiO2 composite material; (4) Add PS / SiO2 composite material, deionized water, copper salt, alkaline solution and reducing agent to a reactor vessel and react at 40-60℃ for 8-10h. Filter the reaction product and collect the solid material. After washing and drying the solid material, PS / SiO2 / Cu composite material is obtained, which is PS composite material. The mass ratio of the PS / SiO2 composite material, deionized water, copper salt, alkaline solution, and sodium borohydride is (30-40):(160-200):(12-16):(10-18):(0.2-0.6).

2. The antibacterial polystyrene composite material according to claim 1, characterized in that: In step (1), the initiator is sodium persulfate; the orthosilicate compound is butyl orthosilicate; the mass ratio of styrene, deionized water, sodium persulfate, anhydrous ethanol and butyl orthosilicate is (40-60):(180-240):(0.1-0.3):(30-40):(16-20).

3. The antibacterial polystyrene composite material according to claim 1, characterized in that: In step (2), the drying temperature is 40-60℃ and the time is 4-6h.

4. The antibacterial polystyrene composite material according to claim 1, characterized in that: In step (4), the reducing agent is sodium borohydride; the copper salt is copper nitrate, copper sulfate or copper phosphate; and the alkaline solution is ammonia or sodium hydroxide solution.

5. The antibacterial polystyrene composite material according to claim 1, characterized in that: In step (4), the drying temperature is 40-60℃ and the time is 4-6h.

6. The antibacterial polystyrene composite material according to claim 1, characterized in that: The antioxidant is at least one of antioxidant 168, antioxidant 1010, and antioxidant 1330.

7. The method for preparing the antibacterial polystyrene composite material according to any one of claims 1-6, characterized in that: Includes the following steps: (1) Weigh 80-100 parts of PS, 8-12 parts of PS composite material, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture; (2) The mixture obtained in step (1) is melt-extruded by a twin-screw extruder and then granulated to obtain antibacterial polystyrene composite material.

8. The method for preparing the antibacterial polystyrene composite material according to claim 7, characterized in that: The twin-screw extruder includes six temperature zones arranged in sequence: Zone 1, 160–180°C; Zone 2, 210–250°C; Zone 3, 210–250°C; Zone 4, 210–250°C; Zone 5, 210–250°C; and Zone 6, 210–250°C. The die temperature of the twin-screw extruder is 210–250°C, and the screw speed is 200–280 r / min.

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