Antibacterial plastic track material and preparation method thereof

Abstract

The invention discloses an antibacterial plastic track material and a preparation method thereof, and belongs to the technical field of plastic track materials. The water-based paint is prepared from the following raw materials in parts by weight: 45 to 55 parts of toluene diisocynate, 15 to 25 parts of polytetramethylene ether glycol, 0.5 to 1.5 parts of catalyst, 24 to 36 parts of filler, 8 to 14 parts of pigment, 4 to 6 parts of antioxidant, 6 to 18 parts of multi-effect antibacterial agent, 30 to 40 parts of acetone, 2 to 4 parts of 1, 4-butanediol and 3 to 6 parts of defoaming agent. According to the prepared runway material, the nano silicon dioxide is added into the raw materials, so that the ultraviolet resistance, the wear resistance and the mechanical property of the material can be improved; the hindered phenol antioxidant is added into the raw materials, so that the oxidation resistance of the material can be improved; wherein molecules of the multi-effect antibacterial agent contain various functional groups, so that the waterproofness and antibacterial property of the material can be greatly enhanced, and the performance is long-lasting and stable; therefore, the invention has important application value in the technical field of plastic track materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of plastic track materials, and in particular, relates to an antibacterial plastic track material and a preparation method thereof. Background Art

[0002] The plastic track, also known as the all-weather track for athletics, is a common surface material for modern sports venues. It has a variety of characteristics and application ranges. It is usually composed of polyurethane prepolymer, mixed polyether, waste tire rubber, EPDM rubber particles or PU particles, pigments, additives, and fillers. The plastic track has the characteristics of good flatness, high compressive strength, appropriate hardness and elasticity, and stable physical properties. It is conducive to the athletes' speed and technology, effectively improving sports performance and reducing the rate of falls.

[0003] The application of plastic track materials directly affects the performance and service life of the plastic track. The material of the existing plastic track is mainly solvent-based polyurethane (such as solvent-based TDI polyurethane, solvent-based MDI polyurethane). Although the plastic track prepared with the current plastic track materials has good performance, it is easy to reduce the quality of the plastic track after long-term use and weathering in the natural environment. This requires high weather resistance of the plastic track material, and there are a large number of pores distributed on the surface of the plastic track. The track can be cleaned only by drainage, which is easy to breed bacteria in the absence of sunlight. If it comes into contact with the human body, it is easy to affect health. Therefore, it is urgent to solve the above problems to meet the higher demands in the field of plastic track material technology. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide an antibacterial plastic track material 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 an antibacterial plastic track material comprises the following steps:

[0007] In a reaction kettle, add preheated toluene diisocyanate, then introduce nitrogen to expel the air in the kettle, then add polytetramethylene ether glycol, catalyst, filler, pigment, antioxidant, multi-effect antibacterial agent and acetone and stir to mix evenly, control the temperature in the kettle at 40-50°C, and keep it warm for 2-3 hours; then add 1,4-butanediol (BDO, chain extender), reflux reaction at 70-80°C for 4-6 hours; after the reaction is completed, add a defoaming agent, and high-speed shear for 0.5-1 hour to obtain an antibacterial plastic track material.

[0008] Furthermore, the raw materials are calculated in parts by weight as follows: 45-55 parts of toluene diisocyanate, 15-25 parts of polytetramethylene ether glycol, 0.5-1.5 parts of catalyst, 24-36 parts of filler, 8-14 parts of pigment, 4-6 parts of antioxidant, 6-18 parts of multi-effect antibacterial agent, 30-40 parts of acetone, 2-4 parts of 1,4-butanediol, and 3-6 parts of defoaming agent.

[0009] Furthermore, the preheating temperature is 60-70°C.

[0010] Furthermore, the catalyst is one of stannous octoate and dibutyltin oxide.

[0011] Furthermore, the defoaming agent is a silicone defoaming agent.

[0012] Furthermore, the antioxidant is a hindered phenol antioxidant.

[0013] Furthermore, the filler comprises nano-silicon dioxide, EPDM particles and PU particles in a mass ratio of 3:2:1.

[0014] Adding nano-silica to the filler, as a nano-material, has a certain effect on improving the material's UV resistance, and can also enhance the material's wear resistance and mechanical properties; hindered phenol antioxidants can provide active hydrogen atoms, capture peroxyl radicals, and can greatly enhance the material's antioxidant properties.

[0015] Furthermore, the multi-effect antibacterial agent is prepared by the following steps:

[0016] S1. In a four-necked flask equipped with a thermometer and a reflux stirring device, allyl chloride and N,N-dimethylformamide were stirred and mixed uniformly, and then 4-pyridinecarboxaldehyde was added dropwise. The reaction temperature was controlled to 65°C, and the reflux reaction was continued for 6 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain intermediate 1; the ratio of allyl chloride, N,N-dimethylformamide and 4-pyridinecarboxaldehyde was 7.6 g:100 mL:10.7 g;

[0017] Allyl chloride reacts with 4-pyridinecarboxaldehyde to form intermediate 1. The specific reaction process is as follows:

[0018]

[0019] S2. In a three-necked flask equipped with a stirring device, the intermediate 1, bisaminopropyl polydimethylsiloxane, piperidine (condensing agent) and toluene were mixed and stirred uniformly, and the temperature of the device was controlled at 70° C. The reaction was kept warm for 6 hours. After the reaction was completed, the mixture was naturally cooled and the solvent was removed by distillation under reduced pressure to obtain the intermediate 2; the ratio of the amount of the intermediate 1, bisaminopropyl polydimethylsiloxane, piperidine and toluene was 31.1 g:10 g:30 mL:100 mL;

[0020] Under the action of the condensing agent, the amino group on the bisaminopropyl polydimethylsiloxane condenses with the aldehyde group on the intermediate 1 to form an imine group (C=N Schiff base structure) to obtain the intermediate 2; the specific reaction process is as follows:

[0021]

[0022] S3. In a three-necked flask, the intermediate 2, azobisisobutyronitrile (AIBN) and N,N-dimethylformamide were stirred and mixed evenly, and then 3-mercaptopropanol was added dropwise, and the temperature of the system was maintained at 75°C. The reaction was carried out for 6 hours. After the reaction was completed, part of the solvent was first removed by rotary evaporation, 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 a multi-effect antibacterial agent; the ratio of the amount of intermediate 2, azobisisobutyronitrile, N,N-dimethylformamide, and 3-mercaptopropanol was 10g:0.2g:100mL:19.1g;

[0023] Under the action of AIBN, the unsaturated carbon-carbon double bond on intermediate 2 undergoes a thiol-ene click reaction with the thiol group on 3-mercaptopropanol to obtain a multi-effect antibacterial agent.

[0024] The prepared multi-effect antibacterial agent is centered on polysiloxane. The Si-O-Si bond in the polysiloxane structure is very stable and has both organic and inorganic properties, which can give the runway material significant waterproof properties. In addition, the multi-effect antibacterial agent also contains Schiff base and pyridinium quaternary ammonium salt structures, among which the Schiff base structure can interact with proteins and enzymes to hinder the synthesis of bacterial nucleotides and amino acids. Pyridinium quaternary ammonium salt is a new type of quaternary ammonium salt with a more concentrated positive charge and stronger bactericidal ability, avoiding the problem of bacterial resistance caused by the long-term use of quaternary ammonium salt antibacterial agents in large quantities. It can synergize with Schiff base to greatly enhance the antibacterial properties of the material. In addition, the multi-effect antibacterial agent is a large molecule and is not easy to precipitate compared to small molecule antibacterial agents, and its performance is long-lasting and stable. The finally prepared multi-effect antibacterial agent contains two hydroxyl groups, so it can participate in the isocyanate polymerization reaction under the action of a catalyst and connect to the polyurethane macromolecular chain, further improving the stability of the multi-effect antibacterial agent.

[0025] Beneficial effects of the present invention:

[0026] 1. The runway material prepared by the present invention has nano-silicon dioxide added to the raw materials, which can improve the material's UV resistance, wear resistance and mechanical properties;

[0027] 2. Adding hindered phenol antioxidants to the raw materials can improve the antioxidant properties of the runway materials;

[0028] 3. Through a series of reactions, a multi-effect antibacterial agent is prepared. The multi-effect antibacterial agent molecules contain various functional groups, which can greatly enhance the waterproofness and antibacterial properties of the material, and the performance is long-term and stable;

[0029] Therefore, the runway material prepared by the present invention can greatly improve the weather resistance of the runway material by adding a variety of functional raw materials. The comprehensive performance of these raw materials can also enhance the antibacterial properties of the material, and the multi-effect antibacterial agent can also enhance the antibacterial properties of the material, which has important application value in the field of plastic runway material technology. DETAILED DESCRIPTION

[0030] 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.

[0031] Embodiment 1

[0032] Preparation of multi-effect antibacterial agent:

[0033] S1. In a four-necked flask equipped with a thermometer and a reflux stirring device, 7.6 g of allyl chloride and 100 mL of N,N-dimethylformamide were stirred and mixed uniformly, and then 10.7 g of 4-pyridinecarboxaldehyde was added dropwise. The reaction temperature was controlled to 65° C. and the reaction was refluxed for 6 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain intermediate 1.

[0034] S2, in a three-necked flask equipped with a stirring device, 31.1g of intermediate 1, 10g of bisaminopropyl polydimethylsiloxane (produced by Guangzhou Qixu Chemical Co., Ltd.), 30mL of piperidine and 100mL of toluene were mixed and stirred evenly, and the temperature of the device was controlled at 70°C, and the reaction was kept warm for 6h. After the reaction was completed, it was naturally cooled and the solvent was removed by distillation under reduced pressure to obtain intermediate 2;

[0035] S3. In a three-necked flask, stir and mix 10 g of intermediate 2, 0.2 g of azobisisobutyronitrile and 100 mL of N,N-dimethylformamide, then drop 19.1 g of 3-mercaptopropanol, maintain the temperature of the system at 75°C, and react for 6 hours. After the reaction, first remove part of the solvent by rotary evaporation, and then purify by column chromatography (the eluent is a mixed solvent of petroleum ether / ethyl acetate in a volume ratio of 5:1), and remove the eluent by rotary evaporation to obtain a multi-effect antibacterial agent.

[0036] Embodiment 2

[0037] Preparation of multi-effect antibacterial agent:

[0038] S1. In a four-necked flask equipped with a thermometer and a reflux stirring device, 15.2 g of allyl chloride and 200 mL of N,N-dimethylformamide were stirred and mixed uniformly, and then 21.4 g of 4-pyridinecarboxaldehyde was added dropwise. The reaction temperature was controlled to 65° C. and the reflux reaction was carried out for 6 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain intermediate 1.

[0039] S2, in a three-necked flask equipped with a stirring device, 62.2g of intermediate 1, 20g of bisaminopropyl polydimethylsiloxane (produced by Guangzhou Qixu Chemical Co., Ltd.), 60mL of piperidine and 200mL of toluene were mixed and stirred evenly, and the temperature of the device was controlled at 70°C, and the reaction was kept warm for 6h. After the reaction was completed, it was naturally cooled and the solvent was removed by distillation under reduced pressure to obtain intermediate 2;

[0040] S3. In a three-necked flask, stir and mix 20 g of intermediate 2, 0.4 g of azobisisobutyronitrile and 200 mL of N,N-dimethylformamide, then drop 38.2 g of 3-mercaptopropanol, maintain the temperature of the system at 75°C, and react for 6 hours. After the reaction, first remove part of the solvent by rotary evaporation, and then purify by column chromatography (the eluent is a mixed solvent of petroleum ether / ethyl acetate in a volume ratio of 5:1), and remove the eluent by rotary evaporation to obtain a multi-effect antibacterial agent.

[0041] Embodiment 3

[0042] In a reaction kettle, 45g of toluene diisocyanate preheated to 60°C was added, and nitrogen was introduced to remove the air in the kettle. Then, 15g of polytetramethylene ether glycol, 0.5g of stannous octoate, 24g of filler (12g of nano-silicon dioxide, 8g of EPDM particles and 4g of PU particles), 8g of pigment (red iron oxide), 4g of antioxidant 1010, 6g of the multi-effect antibacterial agent prepared in Example 1 and 30g of acetone were added and stirred to mix evenly, and the temperature in the kettle was controlled at 40°C and kept warm for 2h; then 2g of 1,4-butanediol was added and refluxed at 70°C for 4h; after the reaction was completed, an organosilicon defoamer was added and high-speed shearing was performed for 0.5h to obtain an antibacterial plastic track material.

[0043] Embodiment 4

[0044] In a reaction kettle, 50g of toluene diisocyanate preheated to 65°C was added, and nitrogen was introduced to remove the air in the kettle. Then, 20g of polytetramethylene ether glycol, 1.0g of dibutyltin oxide, 30g of filler (15g of nano-silicon dioxide, 10g of EPDM particles and 5g of PU particles), 11g of pigment (red iron oxide), 5g of antioxidant 1010, 12g of the multi-effect antibacterial agent prepared in Example 2 and 35g of acetone were added and stirred to mix evenly. The temperature in the kettle was controlled at 45°C and kept warm for 3h; then 3g of 1,4-butanediol was added and refluxed at 75°C for 5h. After the reaction was completed, an organosilicon defoamer was added and high-speed shearing was performed for 1h to obtain an antibacterial plastic track material.

[0045] Embodiment 5

[0046] In a reaction kettle, 55g of toluene diisocyanate preheated to 70°C was added, and nitrogen was introduced to remove the air in the kettle. Then, 25g of polytetramethylene ether glycol, 1.5g of dibutyltin oxide, 36g of filler (18g of nano-silicon dioxide, 12g of EPDM particles and 6g of PU particles), 14g of pigment (red iron oxide), 6g of antioxidant 1010, 18g of the multi-effect antibacterial agent prepared in Example 2 and 40g of acetone were added and stirred to mix evenly. The temperature in the kettle was controlled at 50°C and kept warm for 3h; then 4g of 1,4-butanediol was added and refluxed at 80°C for 6h. After the reaction was completed, an organosilicon defoamer was added and high-speed shearing was performed for 1h to obtain an antibacterial plastic track material.

[0047] Comparative Example 1

[0048] The multi-effect antibacterial agent in Example 5 was replaced by a commercially available antibacterial agent of equal quality, and the remaining steps were the same as those in Example 5 to prepare a runway material.

[0049] Comparative Example 2

[0050] Commercially available polyurethane track material was used.

[0051] Embodiments 3, 4, 5, and comparative examples 1 and 2 were made into corresponding shapes according to different test standards, and the following performance tests were performed:

[0052] The national standard GB / T 10654-2001 "Determination of tensile strength and elongation at break of polymer porous elastic materials" was used to measure the tensile properties of the samples before and after water treatment, and the tensile strength retention rate was calculated; tensile strength retention rate = tensile strength after test / tensile strength before test × 100%; Water treatment: immerse the sample in water, 55℃ water bath for 12h;

[0053] Weather resistance test: Place the sample outdoors and observe the state of the sample after 300 hours;

[0054] The antibacterial rates of Staphylococcus aureus and Escherichia coli of the samples were determined using QB / T 2591-2003A "Test Methods and Antibacterial Effects of Antibacterial Plastics", and the antibacterial rates of Examples 3, 4, 5 and Comparative Example 1 after standing at room temperature for 300 days were determined;

[0055] The measured results are shown in the following table:

[0056]

[0057]

[0058] It can be seen from the above table that the runway material prepared in the embodiment of the present invention has excellent mechanical properties and weather resistance, higher antibacterial properties than the control example, and long-term stable performance, and has important application value in the field of plastic runway material technology.

[0059] 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 can be combined in any one or more embodiments or examples in a suitable manner.

[0060] 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 an antibacterial plastic track material, characterized in that: The following steps are involved: In a reaction kettle, add preheated toluene diisocyanate, then introduce nitrogen to expel the air in the kettle, then add polytetramethylene ether glycol, catalyst, filler, pigment, antioxidant, multi-effect antibacterial agent and acetone and stir to mix evenly, control the temperature in the kettle at 40-50°C, and keep it warm for 2-3 hours; then add 1,4-butanediol, and reflux at 70-80°C for 4-6 hours; after the reaction is completed, add a defoaming agent, and high-speed shear for 0.5-1 hour to obtain an antibacterial plastic track material.

2. The method for preparing an antibacterial plastic track material according to claim 1, characterized in that: The multi-effect antibacterial agent is prepared by the following steps: S1. After allyl chloride and N,N-dimethylformamide are stirred and mixed evenly, 4-pyridinecarboxaldehyde is added dropwise, and the mixture is refluxed at 65° C. for reaction 6. After the reaction is completed, the mixture is distilled under reduced pressure to obtain intermediate 1; S2, after mixing and stirring the intermediate 1, bis-aminopropyl polydimethylsiloxane, piperidine and toluene, the temperature of the device is controlled at 70°C, and the reaction is kept warm for 6 hours. After the reaction is completed, the device is naturally cooled and distilled under reduced pressure to obtain the intermediate 2; S3. Stir and mix the intermediate 2, azobisisobutyronitrile and N,N-dimethylformamide evenly, then drop 3-mercaptopropanol, maintain the temperature of the system at 75°C, and react for 6 hours. After the reaction is completed, perform rotary evaporation, purify by column chromatography, and rotary evaporation to obtain a multi-effect antibacterial agent.

3. The method for preparing an antibacterial plastic track material according to claim 2, characterized in that: In step S1, the ratio of allyl chloride, N,N-dimethylformamide and 4-pyridinecarboxaldehyde is 7.6 g:100 mL:10.7 g.

4. The method for preparing an antibacterial plastic track material according to claim 2, characterized in that: In step S2, the ratio of the amount of intermediate 1, bisaminopropyl polydimethylsiloxane, piperidine and toluene is 31.1 g:10 g:30 mL:100 mL.

5. The method for preparing an antibacterial plastic track material according to claim 2, characterized in that: In step S3, the ratio of the amount of intermediate 2, azobisisobutyronitrile, N,N-dimethylformamide, and 3-mercaptopropanol is 10 g:0.2 g:100 mL:19.1 g.

6. The method for preparing an antibacterial plastic track material according to claim 1, characterized in that: The raw materials are calculated in parts by weight as follows: 45-55 parts of toluene diisocyanate, 15-25 parts of polytetramethylene ether glycol, 0.5-1.5 parts of catalyst, 24-36 parts of filler, 8-14 parts of pigment, 4-6 parts of antioxidant, 6-18 parts of multi-effect antibacterial agent, 30-40 parts of acetone, 2-4 parts of 1,4-butanediol and 3-6 parts of defoaming agent.

7. The method for preparing an antibacterial plastic track material according to claim 1, characterized in that: The catalyst is one of stannous octoate and dibutyltin oxide.

8. The method for preparing an antibacterial plastic track material according to claim 1, characterized in that: The preheating temperature is 60-70℃.

9. The method for preparing an antibacterial plastic track material according to claim 1, characterized in that: The filler comprises nano silicon dioxide, EPDM particles and PU particles in a mass ratio of 3:2:

1. 10.An antibacterial plastic track material, characterized in that: Prepared according to the method according to any one of claims 1 to 9.

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