High-antibacterial PVC plate and preparation method thereof

Abstract

The invention discloses a highly antibacterial PVC plate and a preparation method thereof, and belongs to the technical field of PVC plates. Comprising the following raw materials in parts by weight: 70-80 parts of SG5 type PVC resin, 16-22 parts of calcium carbonate, 15-25 parts of chlorinated polyethylene, 18-28 parts of acrylic resin, 7-21 parts of a multi-effect antibacterial agent and 4-6 parts of a lubricant. Wherein calcium carbonate can improve the processing performance of PVC and enhance the mechanical property of the board; the chlorinated polyethylene can enhance the aging resistance and flexibility of the plate; wherein the acrylic resin can enhance the processability, aging resistance and flexibility of the PVC; the multi-effect antibacterial agent can enhance the antibacterial property, heat resistance and flexibility of the plate, belongs to macromolecules and is stable in performance; therefore, the prepared PVC plate has excellent processability, aging resistance and mechanical property, has stable and efficient antibacterial property, heat resistance and flexibility, and has important application value in the technical field of PVC plates.

Description

Technical Field

[0001] The present invention belongs to the technical field of PVC sheets, and in particular, relates to a highly antibacterial PVC sheet and a preparation method thereof. Background Art

[0002] At present, with the development of social economy, people's living standards have been greatly improved, and the requirements for living environment and quality are getting higher and higher. In addition, with the international emphasis on environmental protection, traditional wooden decorative and decoration materials have gradually been replaced by artificial materials. PVC plastic sheet is one of the products. Polyvinyl chloride is a material made of vinyl chloride monomer. Due to its excellent chemical corrosion resistance, electrical insulation, flame retardancy, light weight, high strength, easy processing and low cost, compared with traditional plywood and wood board, it is not easy to be affected by moisture and deformation, and is more economical and practical. It has been widely used in decoration, renovation, medical and health care, transportation and other fields.

[0003] PVC can be divided into hard PVC and soft PVC according to its physical properties. Hard PVC is mainly used for building pipes, doors and windows, plastic bottles, packaging materials, etc., while soft PVC is used for cable insulation and home decoration. SG5 PVC is a new type of soft PVC resin launched according to market demand. It has both soft and hard performance requirements and has great application value in the furniture industry. However, due to the inherent defects of PVC, PVC sheets have some quality shortcomings. For example, PVC does not have antibacterial properties. When PVC sheets are damp during the rainy season, they provide a breeding ground for bacteria and viruses, leading to the proliferation of bacteria and viruses. Some of these bacteria and viruses are pathogenic, posing a threat and harm to people's lives and health. Not only that, PVC has poor heat resistance, generally 65-70℃. The above shortcomings limit its development speed and application scope. Therefore, it is urgent to overcome the above problems to meet the higher demands in the field of PVC sheet technology. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a highly antibacterial PVC sheet and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A method for preparing a highly antibacterial PVC sheet comprises the following steps:

[0007] A1. Grind the SG5 PVC resin into powder after drying, then add it into a hot mixer with calcium carbonate, chlorinated polyethylene (CPE), acrylic resin (ACR), multi-effect antibacterial agent and lubricant, heat it to 120℃ and stir at high speed to mix, after mixing evenly, put it into a cold mixer and cool it to 45℃ while mixing to form a loose and easy-flowing mixture;

[0008] A2. Add the mixture obtained in step A1 into a twin-screw extruder, heat it to 120-130°C and extrude it into a mold for initial shaping, then pull it into a dry-wet shaping mold, and then cut it after vacuum cooling to obtain a highly antibacterial PVC sheet.

[0009] Furthermore, the raw materials are calculated in parts by weight as follows: 70-80 parts of SG5 type PVC resin, 16-22 parts of calcium carbonate, 15-25 parts of chlorinated polyethylene, 18-28 parts of acrylic resin, 7-21 parts of multi-effect antibacterial agent, and 4-6 parts of lubricant.

[0010] Furthermore, the lubricant is one of paraffin and stearamide.

[0011] Furthermore, the twin-screw extruder is a twin-screw extruder that rotates outward in opposite directions and has a degassing device.

[0012] Adding calcium carbonate can increase the fluidity of PVC, improve processing performance, and can also serve as a filler to enhance the mechanical properties of the board; introducing chlorinated polyethylene can enhance the aging resistance and certain flexibility of the board; finally, the addition of acrylic resin can further enhance the processing properties of PVC and the aging resistance of the board, and can greatly enhance the flexibility of the board.

[0013] Furthermore, the multi-effect antibacterial agent is prepared by the following steps:

[0014] S1. In a three-necked flask equipped with a stirring device, 4-pyridinecarboxaldehyde, n-decylamine, piperidine (condensing agent) and N,N-dimethylformamide were mixed, and the mixture was stirred continuously until the mixture was uniformly mixed. The reaction temperature was controlled to be 65°C, and the reaction was kept warm for 5 hours. After the reaction was completed, part of the solvent was removed by distillation under reduced pressure, and then purified by column chromatography (the eluent was a mixed solvent of ethyl acetate / petroleum ether in a volume ratio of 1:4), the eluent was removed by rotary evaporation, and vacuum dried to obtain intermediate 1; the ratio of the amount of 4-pyridinecarboxaldehyde, n-decylamine, piperidine and N,N-dimethylformamide was 10.7 g:15.7 g:15 mL:100 mL;

[0015] Under the action of the condensing agent, the amino group on the n-decylamine condenses with the aldehyde group on the 4-pyridinecarboxaldehyde to form an imine group (C=N Schiff base structure) to obtain intermediate 1; the specific reaction process is as follows:

[0016]

[0017] S2. Under nitrogen protection at room temperature, add intermediate 1 and N,N-dimethylformamide to a three-necked flask equipped with a stirring device, stir and mix evenly, then slowly drop 4-bromo-1-butene. After the dropwise addition is completed, place the device in a water bath, stir and react for 6 hours at 70°C in a water bath, and after the reaction is completed, remove part of the solvent by vacuum distillation, and then purify by column chromatography (the eluent is a mixed solvent of petroleum ether / ethyl acetate, and the volume ratio of the two is 5:1), and remove the eluent by rotary evaporation to obtain intermediate 2; the ratio of the amount of intermediate 1, N,N-dimethylformamide, and 4-bromo-1-butene is 24.6g:150mL:13.3g;

[0018] Intermediate 1 undergoes quaternization reaction with 4-bromo-1-butene to obtain intermediate 2; the specific reaction process is as follows:

[0019]

[0020] S3. Add hydrogenated silicone oil, N,N-dimethylformamide and Speier catalyst to a three-necked flask equipped with a stirring reflux device, stir at room temperature for 30 minutes, add intermediate 2, raise the temperature to 80°C, and keep the reaction for 8 hours. Stir continuously during the reaction. After the reaction is completed, stop heating, wait for the device to cool to room temperature, stir for 5 hours, filter, and remove the solvent by rotary evaporation to obtain a multi-effect antibacterial agent; the ratio of hydrogenated silicone oil, N,N-dimethylformamide, Speier catalyst, and intermediate 2 is 10g:100mL:0.3mL:16.4g;

[0021] Under the catalysis of Speier catalyst, hydrogen-containing silicone oil and the unsaturated carbon-carbon double bond of intermediate 2 undergo a hydrosilylation reaction to obtain a multi-effect antibacterial agent; the specific reaction process is as follows:

[0022]

[0023] The prepared multi-effect antibacterial agent is mainly composed of polysiloxane chains, and the main chain of the polysiloxane is composed of silicon-oxygen bonds (Si-O bonds). The bond energy of this bond is relatively high, and the heat resistance of the PVC matrix can be greatly enhanced. In addition, the multi-effect antibacterial agent contains pyridinium quaternary ammonium salt and Schiff base antibacterial components, wherein the pyridinium quaternary ammonium salt is a new type of quaternary ammonium salt, and its positive charge is more concentrated, and the bactericidal ability is stronger, which avoids the problem of bacterial resistance caused by the long-term use of quaternary ammonium salt antibacterial agents in large quantities, and can greatly enhance the antibacterial performance of the matrix; and the Schiff base structure can interact with bacterial proteins and enzymes, so that the synthesis of bacterial nucleotides and amino acids is hindered, and it has a synergistic effect with the pyridinium quaternary ammonium salt, and greatly enhances the antibacterial performance of the matrix; finally, the long carbon chain introduced into the multi-effect antibacterial agent is a methylene chain segment, which can improve the flexibility of the matrix, and can also be interspersed in the polymer chain of the matrix, and is more closely connected with the matrix, thereby improving the stability of the multi-effect antibacterial agent;

[0024] It should be noted that the prepared multi-effect antibacterial agent is a large molecule, which is less likely to migrate and seep out than small molecule antibacterial agents and has better stability.

[0025] Beneficial effects of the present invention:

[0026] 1. The PVC sheet prepared by the present invention improves the processing performance of PVC and enhances the mechanical properties of the sheet by adding calcium carbonate as a filler;

[0027] 2. The addition of chlorinated polyethylene can enhance the aging resistance and flexibility of the board;

[0028] 3. The addition of acrylic resin can further enhance the processability, aging resistance and flexibility of PVC;

[0029] 4. The multi-effect antibacterial agent molecules contain synergistic antibacterial active ingredients, as well as ingredients that can enhance the heat resistance and flexibility of the board. They are macromolecules with stable performance and are not easy to fall off.

[0030] Therefore, the PVC sheet prepared by the present invention improves its processability, aging resistance and mechanical properties by adding multiple functional raw materials, and has stable and efficient antibacterial properties, heat resistance and flexibility, and has important application value in the field of PVC sheet technology. DETAILED DESCRIPTION

[0031] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] Embodiment 1

[0033] Preparation of multi-effect antibacterial agent:

[0034] S1. In a three-necked flask equipped with a stirring device, 10.7 g of 4-pyridinecarboxaldehyde, 15.7 g of n-decylamine, 15 mL of piperidine and 100 mL of N,N-dimethylformamide were mixed and stirred continuously until the mixture was uniformly mixed. The reaction temperature was controlled to be 65° C. and the reaction was kept warm for 5 hours. After the reaction was completed, part of the solvent was distilled off under reduced pressure, and then purified by column chromatography (the eluent was a mixed solvent of ethyl acetate / petroleum ether in a volume ratio of 1:4), the eluent was removed by rotary evaporation, and vacuum drying was performed to obtain intermediate 1;

[0035] S2, under nitrogen protection at room temperature, in a three-necked flask equipped with a stirring device, add 24.6g of intermediate 1 and 150mL of N,N-dimethylformamide, stir and mix evenly, then slowly drop 13.3g of 4-bromo-1-butene, after the dropwise addition is completed, place the device in a water bath, stir and react for 6h in a water bath at 70°C, after the reaction is completed, remove part of the solvent by distillation under reduced pressure, and then purify by column chromatography (the eluent is a mixed solvent of petroleum ether / ethyl acetate, the volume ratio of the two is 5:1), and remove the eluent by rotary evaporation to obtain intermediate 2;

[0036] S3. Add 10 g of hydrogenated silicone oil, 100 mL of N,N-dimethylformamide and 0.3 mL of Speier catalyst into a three-necked flask equipped with a stirring reflux device. After stirring at room temperature for 30 min, add 16.4 g of intermediate 2, raise the temperature to 80°C, and keep the reaction warm for 8 h. Stir continuously during the reaction. After the reaction is completed, stop heating, wait for the device to cool to room temperature, stir for 5 h, filter, and rotary evaporate to remove the solvent to obtain a multi-effect antibacterial agent; wherein the Speier catalyst is prepared by dissolving 0.1 g of chloroplatinic acid in 100 mL of isopropanol and stirring at room temperature.

[0037] Embodiment 2

[0038] Preparation of multi-effect antibacterial agent:

[0039] S1, in a three-necked flask equipped with a stirring device, 21.4g 4-pyridinecarboxaldehyde, 31.4g n-decylamine, 30mL piperidine and 200mL N, N-dimethylformamide were mixed, and the mixture was stirred continuously until the mixture was uniformly mixed. The reaction temperature was controlled to 65°C, and the mixture was kept warm for 5h. After the reaction was completed, part of the solvent was removed by distillation under reduced pressure, and then purified by column chromatography (the eluent was a mixed solvent of ethyl acetate / petroleum ether, and the volume ratio of the two was 1:4), the eluent was removed by rotary evaporation, and the mixture was dried in vacuo to obtain intermediate 1;

[0040] S2, under nitrogen protection at room temperature, 49.2g of intermediate 1 and 300mL of N,N-dimethylformamide were added to a three-necked flask equipped with a stirring device, and the mixture was stirred and mixed evenly, and then 26.6g of 4-bromo-1-butene was slowly added dropwise. After the addition was completed, the device was placed in a water bath, and stirred for 6h under a water bath condition of 70°C. After the reaction was completed, part of the solvent was distilled off under reduced pressure, and then purified by column chromatography (the eluent was a mixed solvent of petroleum ether / ethyl acetate, and the volume ratio of the two was 5:1), and the eluent was removed by rotary evaporation to obtain intermediate 2;

[0041] S3. Add 20 g of hydrogenated silicone oil, 200 mL of N,N-dimethylformamide and 0.6 mL of Speier catalyst into a three-necked flask equipped with a stirring reflux device. After stirring at room temperature for 30 min, add 32.8 g of intermediate 2, raise the temperature to 80°C, and keep the reaction warm for 8 h. Stir continuously during the reaction. After the reaction is completed, stop heating, wait for the device to cool to room temperature, stir for 5 h, filter, and rotary evaporate to remove the solvent to obtain a multi-effect antibacterial agent; wherein the Speier catalyst is prepared by dissolving 0.1 g of chloroplatinic acid in 100 mL of isopropanol and stirring at room temperature.

[0042] Embodiment 3

[0043] A1. 70g of SG5 PVC resin was dried and ground into powder, and then added to a hot mixer with 16g of calcium carbonate, 15g of chlorinated polyethylene, 18g of acrylic resin, 7g of the multi-effect antibacterial agent prepared in Example 1 and 4g of paraffin wax, heated to 120°C and stirred at high speed for mixing. After mixing evenly, the mixture was placed in a cold mixer and cooled to 45°C while mixing to form a loose, easy-flowing mixture;

[0044] A2. Add the mixture obtained in step A1 into a counter-rotating outward-rotating twin-screw extruder with an exhaust device, heat it to 120°C and extrude it into a mold for initial shaping, then pull it into a dry-wet shaping mold, and then cut it after vacuum cooling to obtain a highly antibacterial PVC sheet.

[0045] Embodiment 4

[0046] A1. 75g of SG5 PVC resin was dried and ground into powder, and then added to a hot mixer with 19g of calcium carbonate, 20g of chlorinated polyethylene, 23g of acrylic resin, 14g of the multi-effect antibacterial agent prepared in Example 2 and 5g of stearamide, heated to 120°C and stirred at high speed for mixing. After mixing evenly, the mixture was placed in a cold mixer and cooled to 45°C while mixing to form a loose, easy-flowing mixture;

[0047] A2. Add the mixture obtained in step A1 into a counter-rotating outward-rotating twin-screw extruder with an exhaust device, heat it to 125°C and extrude it into a mold for initial shaping, then pull it into a dry-wet shaping mold, and then cut it after vacuum cooling to obtain a highly antibacterial PVC sheet.

[0048] Embodiment 5

[0049] A1. 80g of SG5 PVC resin was dried and ground into powder, and then added to a hot mixer with 22g of calcium carbonate, 25g of chlorinated polyethylene, 28g of acrylic resin, 21g of the multi-effect antibacterial agent prepared in Example 2 and 6g of stearamide, heated to 120°C and stirred at high speed for mixing. After mixing evenly, the mixture was placed in a cold mixer and cooled to 45°C while mixing to form a loose, easy-flowing mixture;

[0050] A2. Add the mixture obtained in step A1 into a counter-rotating outward-rotating twin-screw extruder with an exhaust device, heat it to 130°C and extrude it into a mold for initial shaping, then pull it into a dry-wet shaping mold, and then cut it after vacuum cooling to obtain a highly antibacterial PVC sheet.

[0051] Comparative Example 1

[0052] The multi-effect antibacterial agent in Example 5 was replaced by a commercially available quaternary ammonium salt antibacterial agent of equal quality, and the remaining steps were the same as those in Example 5 to obtain a PVC sheet.

[0053] Comparative Example 2

[0054] Commercially available PVC sheets were used.

[0055] Embodiments 3, 4, 5 and comparative examples 1 and 2 were made into corresponding shapes according to different standards and the following performance tests were performed:

[0056] The oxidation induction time was determined using the national standard GB / T 19466.6-2009 "Plastic Differential Scanning Calorimetry";

[0057] The notched impact strength was measured according to the national standard GB / T 1043.1-2008 "Determination of impact properties of simply supported beams of plastics - Part 1: Non-instrumented impact test"; the sample was then placed in an environment of 120°C and oxidized with hot air for 72 hours, and the notched impact strength retention rate was measured; notched impact strength retention rate = notched impact strength after test / notched impact strength before test × 100%;

[0058] QB / T 2591-2003A "Test Methods and Antibacterial Effects of Antibacterial Plastics" was used to determine the antibacterial rates of Staphylococcus aureus and Escherichia coli before and after the samples were left at room temperature for 200 days.

[0059] The measured results are shown in the following table:

[0060]

[0061]

[0062] It can be seen from the above table that the PVC sheet prepared in the embodiment of the present invention has a long oxidation induction time and good aging resistance. Its antibacterial property, heat resistance and flexibility are higher than those of the comparative example. Moreover, after standing at room temperature for 200 days, the embodiment still has excellent antibacterial property. Therefore, the present invention has important application value in the field of PVC sheet technology.

[0063] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0064] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A method for preparing a highly antibacterial PVC sheet, characterized in that: The following steps are involved: A1. Grind the PVC resin into powder after drying, then add it into a hot mixer with calcium carbonate, chlorinated polyethylene, acrylic resin, multi-effect antibacterial agent and lubricant, stir and mix, and after mixing evenly, put it into a cold mixer to mix and cool at the same time to form a loose and easy-flowing mixture; A2. Add the mixture obtained in step A1 into a twin-screw extruder, heat it to the mold for initial shaping and extrude it, pull it into a dry and wet shaping mold, and then cut it after vacuum cooling to obtain a highly antibacterial PVC sheet.

2. The method for preparing a highly antibacterial PVC sheet according to claim 1, characterized in that: The multi-effect antibacterial agent is prepared by the following steps: S1, 4-pyridinecarboxaldehyde, n-decylamine, piperidine and N,N-dimethylformamide were mixed, and the mixture was stirred continuously until the mixture was uniformly mixed, and the mixture was kept at 65°C for 5 hours. After the reaction was completed, the mixture was distilled under reduced pressure, purified by column chromatography, rotary evaporated, and dried in vacuo to obtain intermediate 1; S2. Under nitrogen protection at room temperature, the intermediate 1 and N,N-dimethylformamide were stirred and mixed evenly, and 4-bromo-1-butene was slowly added dropwise. After the addition was completed, the mixture was placed in a water bath and stirred at 70°C for 6 hours. After the reaction was completed, the mixture was distilled under reduced pressure, purified by column chromatography, and rotary evaporated to obtain the intermediate 2. S3. Stir hydrogenated silicone oil, N,N-dimethylformamide and Speier catalyst at room temperature for 30 minutes, then add intermediate 2 and react at 80°C for 8 hours with continuous stirring. After the reaction is complete, stop heating and wait for the device to cool to room temperature. Stir for 5 hours, filter and evaporate to remove the solvent to obtain a multi-effect antibacterial agent.

3. The method for preparing a highly antibacterial PVC sheet according to claim 2, characterized in that: In step S1, the ratio of the amount of 4-pyridinecarboxaldehyde, n-decylamine, piperidine and N,N-dimethylformamide is 10.7 g:15.7 g:15 mL:100 mL.

4. The method for preparing a highly antibacterial PVC sheet according to claim 2, characterized in that: In step S2, the ratio of the amount of intermediate 1, N,N-dimethylformamide, and 4-bromo-1-butene is 24.6 g:150 mL:13.3 g.

5. The method for preparing a highly antibacterial PVC sheet according to claim 2, characterized in that: In step S3, the ratio of the amount of hydrogen-containing silicone oil, N,N-dimethylformamide, Speier catalyst, and intermediate 2 is 10 g: 100 mL: 0.3 mL: 16.4 g.

6. The method for preparing a highly antibacterial PVC sheet according to claim 1, characterized in that: The raw materials are calculated in parts by weight as follows: 70-80 parts of PVC resin, 16-22 parts of calcium carbonate, 15-25 parts of chlorinated polyethylene, 18-28 parts of acrylic resin, 7-21 parts of multi-effect antibacterial agent, and 4-6 parts of lubricant.

7. The method for preparing a highly antibacterial PVC sheet according to claim 1, characterized in that: The lubricant is one of paraffin and stearamide.

8. A highly antibacterial PVC sheet, characterized in that: Prepared according to the method according to any one of claims 1 to 7.

Images